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Nanostructuring of Self‐Assembled Porphyrin Networks at a Solid/Liquid Interface: Local Manipulation under Global Control
Author(s) -
Coenen Michiel J. J.,
Khoury Tony,
Crossley Maxwell J.,
Hendriksen Bas L. M.,
Elemans Johannes A. A. W.,
Speller Sylvia
Publication year - 2014
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201402449
Subject(s) - monolayer , scanning tunneling microscope , highly oriented pyrolytic graphite , porphyrin , pyrolytic carbon , graphite , molecule , materials science , self assembly , self assembled monolayer , crystallography , nanotechnology , chemistry , chemical engineering , chemical physics , organic chemistry , pyrolysis , engineering
Molecules of (5,10,15,20‐tetraundecylporphyrinato)‐copper(II) [(TUP)Cu] can self‐assemble into four different polymorphs at the interface between highly oriented pyrolytic graphite and 1‐octanoic acid. Scanning tunneling microscopy (STM) reveals that it is possible to combine the global control over monolayer structure, provided by the composition and concentration of the supernatant solution, with local control, from nanomanipulation by the STM tip. In the initially formed monolayer, with a polymorph composition governed by the concentration of (TUP)Cu in the supernatant solution, the exchange of molecules physisorbed at the solid/liquid interface with those in the liquid is very limited. By using a nanoshaving procedure at the tip, defects are created in the monolayer, and these serve as local manipulation sites to create domains of higher or lower molecular density, and to incorporate a second molecular species, (TUP)Co into the monolayer of (TUP)Cu.